Anthraquinone dyestuffs

ABSTRACT

DYESTUFFS OF THE FORMULA:   1-NH2,2-((1-(HO-CH2-)CYCLOHEX-3-EN-1-YL)-CH2-O-),4-X-   ANTHRAQUINONE   IN WHICH X REPRESENTS A HYDROXY, AMINO OR -NH-SO2R GROUP AND R REPRESENTS AN ALKYL OR ARYL RADICAL EITHER UNSUBSTITUTED OR SUBSTITUTED BY AT LEAST ONE ALKYL RADICAL WHICH MAY CONTAIN UP TO 4 CARBON ATOMS, MIXTURES OF THESE DYESTUFFS, PROCESSES FOR THEIR PREPARATION AND SYNTHETIC OR ARTIFICIAL FIBRES DYED OR PRINTED THEREWITH.

United States Patent 3,763,192 ANTHRAQUIN ONE DYESTUFFS Louis AntoineCabut, Nogent-sur-Oise, France, assignor to Ugine Kuhlmann, Paris,France No Drawing. Filed Jan. 13, 1971, Ser. No. 106,232 Claimspriority, application France, Jan. 29, 1970, 7003083 Int. Cl. C09b 1/52U.S. Cl. 260373 3 Claims ABSTRACT OF THE DISCLOSURE Dyestuffs of theformula:

in which X represents a hydroxy, amino or -NHflO R group and Rrepresents an alkyl or aryl radical either unsubstituted or substitutedby at least one alkyl radical which may contain up to 4 carbon atoms,mixtures of these dyestuffs, processes for their preparation andsynthetic or artificial fibres dyed or printed therewith.

The invention concerns new anthraquinone dyestuffs. According to thisinvention anthraquinone dyestuffs are provided of the general formula:

in which X represents a hydroxy, amino or NHSO R group and R is an alkylor aryl radical either unsubstituted or substituted by at least onealkyl radical which may contain up to 4 carbon atoms.

Anthraquinone compounds of similar constitution having benzyloxy,cyclohexyloxy, 4- or 2-hydroxymethyl cyclohexanemethoxy, or4-hydroxymethyl phenylmethoxy groups in the 2 position are alreadyknown. By comparison with these known compounds the compounds of thepresent invention possess superior tinctorial properties which wereentirely unexpected which are characterized both by an excellentresistance to sublimation and a remarkable afiinity for fibres based onpolyesters.

The dyestuffs of Formula I may be prepared, for example, by the actionof 3-cyclohexene-1,l-dimethanol on an acid falling within the generalformula:

(a) The action of 3-cyclohexene-1,1-dimethanol on compounds of thegeneral formula:

(H) NH: Y Y

Xi (H) in which X, represents a hydroxy or amino group and Y representsa phenoxy or an alkoxy group containing up to 4 carbon atoms, or by (b)The action of 3-cyclohexene-1,l-dimethanol on 1-amino-2-bromo-4-hydroxy-anthraquinone or 1,4-diamino-2-chloro-anthraquinone.

The dyestuffs of Formula I used in the dispersed state either singly orin mixtures are Well fitted for the colouration of synthetic orartificial fibres, more particularly fibres based on polyesters, forexample, those based on polyterephthalates of ethylene glycol. Suchfibres are known on the market, for example, by the trademarks Terylene,Dacron or Tergal.

The dyestutfs according to the invention may be used according to theusual methods of dyeing or printing. They can be applied, for example,by means of dyebaths containing a dispersion of the dyestuff andadvantageously a swelling agent at temperatures around 100 C. or attemperatures above 100 C. in closed apparatus. Pure and full-bodiedshades are obtained which range from pink to red-violet and which arecharacterised by very good fastness to light and excellent fastness tosublimation.

The invention is illustrated by the following examples, in which theparts and the percentages are by weight.

EXAMPLE 1 60 parts of 3-cyclohexene-1,1-dimethanol and 2 parts ofpotassium hydroxide are agitated at 140-150 C. for 1 hour. The mixtureis cooled to 100-110 C. and 8 parts of1-amino-2-phenoxy-4-hydroxy-anthraquinone are added. The mixture is thenheated at 140-150 C. for three hours under nitrogen, cooled to C. anddiluted in 1000 parts of water. A red product is precipitated as well asthe excess cyclohexene-dirnethanol. The solid is filtered 01f, washedwith hot water until the cyclohexene-dimethanol is completelyeliminated, and dried. 8.2 parts of 1- amino-4-hydroxy 2(l-hydroxyrnethyl 3 cyclohexene-l-yl)methoxy-anthraquinone in the formof a red powder are thus obtained.

0.5 part of this powder and 1 part of dinaphthylmethane-disulphonate orsodium are ground in 6 parts of water until a fine dispersion isobtained. This mixture is poured into 3000 parts of Water and 1.5 partsof 2- hydroxy-diphenyl are added. The dyebath thus prepared is heated to60 C. and 100 parts of polyester fibres are introduced. The bath isheated to boiling in a period of 20 minutes and maintained at this foran hour. The fibres are removed from the bath, rinsed in water anddried. They are dyed a pink shade which is very fast to light andremarkably resistant to heat-fixing and creasing.

EXAMPLE 2 50 parts of 3-cyclohexene-l,l-dimethanol and 2.3 parts ofpotassium hydroxide are agitated at 100 C. for 1 hour, then 3.4 parts of1-amino-4-hydroxy-anthraquinone- 2-sulphonate of sodium are added. Themixture is heated at 130-140 C. under nitrogen for 5 hours and is then2. The compound of the formula: poured into 500 parts of water. Thesolid is filtered off NH and washed with hot water to remove the diol. 3parts of 2 V a red powder are thus obtained which melts at 169l71 A C.after crystallisation from chloroform.

In a dispersed state, this dyestuffs dyes fibres based 011,011 onpolyester a pink shade identical with that obtained Y in Example 1, andalso fast to light, heat-fixing and 0 OH creasing.

Example 3 3. The compound of the formula:

10 parts of potassium hydroxide are dissolved in 100 o NHa parts of3-cyclohexene-1,l-dimethanol at 90-100 C. A 3 parts of1-amino-4-(4-methylphenylsulphonylamino)-an- OCH2 thraquinone-Z-sodiumsulphonate are added to this solution in a period of 15 minutes. Thetemperature is main- 15 CHiOH tained at 80-90" C. until the sulphonatedderivative dis- I appears. The product is then diluted with water, thepre- NH-SOQ-CH; cipitate filtered oif, Washed with hot Water and dried.The l-amino 4(methylphenylsulphonylamino)-2-(1-hydroxymethyl-3-cyclohexene-l-yl)rnethoxyanthraquinone References Clted thus obtained dyes fibres based 0npolyesters in a full- UNITED STATES PATENTS 'bodied red shade havingvery good fastness especially to 3 533 129 11 /1970 w et 1 2 37sublimation 2,992,240 7/1961 Lodge 260-380 61211111! & fth f 1 52,773,071 12/ 1956 Pizzarello 260--380 Dyest g? FOREIGN PATENTS a756,261 9/1956 Great Britain 260-380 I t 7Q LORRAINE A. WEINBERGER,Primary Examiner CHHOH R. GERSTL, Assistant Examiner X US. Cl. X.R.

in which X is hydroxy, amino or p-tolylsulfonylamino. 8-39, 40; 260380

